Aromaticity and Extrusion of Benzenoids Linked to [<i>o</i>‐COSAN]<sup>−</sup>: Clar Has the Answer

Poater, Jordi; Viñas, Clara; Olid, David; Solà, Miquel; Teixidor, Francesc

doi:10.1002/ange.202200672

Angewandte Chemie

2022

DOI: 10.1002/ange.202200672

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Aromaticity and Extrusion of Benzenoids Linked to [o‐COSAN]⁻: Clar Has the Answer

Jordi Poater

Clara Viñas

David Olid

et al.

Abstract: Benzene and pyrene can be synthetically linked to [o-COSAN] À keeping their aromaticity. In contrast, naphthalene and anthracene are extruded in the same reaction. We have proven that extrusion is only favorable if the number of Clar's π-sextets remains constant. Thus, Clar has the answer to whether an attached polycyclic aromatic hydrocarbon to [o-COSAN] À is extruded or not.

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Cited by 3 publications

References 48 publications

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Site‐Selective Functionalization of Carboranes at the Electron‐Rich Boron Vertex: Photocatalytic B−C Coupling via a Carboranyl Cage Radical

Chen

Zhao

et al. 2022

Angewandte Chemie

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Functionalization of carboranes in a vertex‐specific manner is a perennial challenge. Here, we report a photocatalytic B−C coupling for the selective functionalization of carboranes at the boron site which is most distal to carbon. This reaction was achieved by the photo‐induced decarboxylation of carborane carboxylic acids to generate boron vertex‐centered carboranyl radicals. Theoretical calculations also demonstrate that the reaction more easily occurs at the boron site bearing higher electron density owing to the lower energy barrier for a single‐electron transfer to generate a carboranyl radical. By using this strategy, a number of functionalized carboranes could be accessed through alkylation, alkenylation, and heteroarylation under mild conditions. Moreover, both a highly efficient blue emitter with a solid‐state luminous efficiency of 42 % and a drug candidate for boron neutron capture therapy (BNCT) containing targeting and fluorine units were obtained.

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Site‐Selective Functionalization of Carboranes at the Electron‐Rich Boron Vertex: Photocatalytic B−C Coupling via a Carboranyl Cage Radical

Chen

Zhao

et al. 2022

Angewandte Chemie

View full text Add to dashboard Cite

show abstract

Site‐Selective Functionalization of Carboranes at the Electron‐Rich Boron Vertex: Photocatalytic B−C Coupling via a Carboranyl Cage Radical

Chen

Zhao

et al. 2022

Angew Chem Int Ed

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Facile Construction of New Hybrid Conjugation via Boron Cage Extension

et al. 2023

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Aromatic polycyclic systems have been extensively utilized as structural subunits for the preparation of various functional molecules. Currently, aromatics-based polycyclic systems are predominantly generated from the extension of two-dimensional (2D) aromatic rings. In contrast, polycyclic compounds based on the extension of three-dimensional (3D) aromatics such as boron clusters are less studied. Here, we report three types of boron cluster-cored tricyclic molecular systems, which are constructed from a 2D aromatic ring, a 3D aromatic nido-carborane, and an alkyne. These new tricyclic compounds can be facilely accessed by Pd-catalyzed B–H activation and the subsequent cascade heteroannulation of carborane and pyridine with an alkyne in an isolated yield of up to 85% under mild conditions without any additives. Computational results indicate that the newly generated ring from the fusion of the 3D carborane, the 2D pyridyl ring, and an alkyne is non-aromatic. However, such fusion not only leads to a 1H chemical shift considerably downfield shifted owing to the strong diatropic ring current of the embedded carborane but also devotes to new/improved physicochemical properties including increased thermal stability, the emergence of a new absorption band, and a largely red-shifted emission band and enhanced emission efficiency. Besides, a number of bright, color-tunable solid emitters spanning over all visible light are obtained with absolute luminescence efficiency of up to 61%, in contrast to aggregation-caused emission quenching of, e.g., Rhodamine B containing a 2D-aromatics-fused structure. This work demonstrates that the new hybrid conjugated tricyclic systems might be promising structural scaffolds for the construction of functional molecules.

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Aromaticity and Extrusion of Benzenoids Linked to [o‐COSAN]⁻: Clar Has the Answer

Cited by 3 publications

References 48 publications

Site‐Selective Functionalization of Carboranes at the Electron‐Rich Boron Vertex: Photocatalytic B−C Coupling via a Carboranyl Cage Radical

Site‐Selective Functionalization of Carboranes at the Electron‐Rich Boron Vertex: Photocatalytic B−C Coupling via a Carboranyl Cage Radical

Site‐Selective Functionalization of Carboranes at the Electron‐Rich Boron Vertex: Photocatalytic B−C Coupling via a Carboranyl Cage Radical

Facile Construction of New Hybrid Conjugation via Boron Cage Extension

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Aromaticity and Extrusion of Benzenoids Linked to [o‐COSAN]−: Clar Has the Answer

Cited by 3 publications

References 48 publications

Site‐Selective Functionalization of Carboranes at the Electron‐Rich Boron Vertex: Photocatalytic B−C Coupling via a Carboranyl Cage Radical

Site‐Selective Functionalization of Carboranes at the Electron‐Rich Boron Vertex: Photocatalytic B−C Coupling via a Carboranyl Cage Radical

Site‐Selective Functionalization of Carboranes at the Electron‐Rich Boron Vertex: Photocatalytic B−C Coupling via a Carboranyl Cage Radical

Facile Construction of New Hybrid Conjugation via Boron Cage Extension

Contact Info

Product

Resources

About

Aromaticity and Extrusion of Benzenoids Linked to [o‐COSAN]⁻: Clar Has the Answer